CN101687743B - Glycerol vaporization method - Google Patents

Glycerol vaporization method Download PDF

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Publication number
CN101687743B
CN101687743B CN200880008695.0A CN200880008695A CN101687743B CN 101687743 B CN101687743 B CN 101687743B CN 200880008695 A CN200880008695 A CN 200880008695A CN 101687743 B CN101687743 B CN 101687743B
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glycerol
bed
fluidized
solid
solution
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Expired - Fee Related
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CN200880008695.0A
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CN101687743A (en
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J·-L·杜博伊斯
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Arkema France SA
Arkema SA
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Arkema SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/0011—Heating features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/14—Evaporating with heated gases or vapours or liquids in contact with the liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/16—Evaporating by spraying
    • B01D1/18—Evaporating by spraying to obtain dry solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/22—Trihydroxylic alcohols, e.g. glycerol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Medicinal Preparation (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)

Abstract

The subject matter of the present invention relates to a vaporization method of aqueous glycerol solutions in a fluidized bed containing an inert solid. The invention provides a method for vaporizing, in a single step, an aqueous glycerol solution and simultaneously eliminating the impurities present in this solution or generated during the evaporation.

Description

The method of evaporating of glycerol
The application's object is the method for evaporating glycerin solution in the fluidized-bed that contains inert solid, the method can remove simultaneously in this solution, exist and evaporative process in the impurity that produces.
Glycerol is a kind of chemical products, i.e. Glycerin, and it can be made by chemosynthesis by propylene, or can in the methanolysis of vegetables oil, produce as by product.
Can carry out the methanolysis of vegetables oil by various technique, especially by using homogeneous catalyst, as the methanol solution of sodium hydroxide or sodium methylate, or use heterogeneous catalyst.About this theme can be with reference to people such as DBallerini the article in the l ' actualit of the 11-12 month in 2002 é chimique.
The methanolysis of vegetables oil produces methyl esters on the one hand, produces on the other hand glycerol.Methyl esters is especially used as fuel or fuel oil is used in the fuel in diesel oil and household fuel.Along with renewable source fuel is developed, the especially exploitation to vegetables oil methyl esters (EMHV), improves the glycerol output that generates thus approach greatly, and glycerol accounts for and transforms 10% of weight of oil.
Be a kind of natural product of renewable source from the glycerol of vegetables oil, therefore more and more can use.Under the background of current New Concept of Green Chemistry, emphasize more and more Sustainable development, make this product increment become more and more useful.
But the production method of manufacturing EMVH causes purity or glycerol high or low and that more or less dilute in water.According to " the Soap and Detergent Association " (Soaps and Detergents:Atheoretical and Practical Review, Miami Beach Fla., 12-14 day in October, 1994, the 6th chapter 172-206 page, editor: L Spitz, AOCS Press, Champaign) definition that adopts, conventionally these purity or high or low glycerin solution are named as to glycerine.Raw glycerine has the composition of approximately 88% glycerol, the water of 9-10% and the impurity of 2-3% conventionally.In particular, it for example can contain impurity, as organic compound, methyl alcohol or the vegetables oil residue of subsalt (sodium salt or sylvite), non-glycerine.In some application of glycerol, the existence of these impurity is harmful to especially for the quality of carried out reaction or final product.For example, in the situation that preparing propenal, the existence of sodium salt or sylvite is harmful to generate third rare aldehyde for the catalytic and dehydration reaction of glycerol, and this is because these salt can be poisoned the acid site of used catalyst.
Therefore, thick glycerin solution or glycerine need to pass through pre-treatment conventionally before use, or purification process is to consider new purposes.
In addition, usually not only need to remove less desirable impurity for considered purposes, also need solution to concentrate, even vaporize water solution, because some commercial run uses the glycerol of vapor form.These operations are very meticulous, because known glycerol can be decomposed, are especially decomposed into propenal, or cause polymkeric substance as Polyglycerine.
The various purification techniques of glycerol are described in existing document.In fact, this is a kind of product with more than 1500 kinds different purposes, requires any extra fine quality, especially has " pharmacopeia " level, and it needs the glycerol that purity is very high.
The purifying to glycerol evaporation is used or the method studied in, to enumerate especially the method for being described by G.B.D ' Souza in J.Am.Oil Chemists ' Soc.1979 November (the 56th volume) 812A, by people such as Steinberner U in Fat.Sci.Technol. (1978), the 8th phase of 89Jahrgang, the method of describing in 297-303 page, and by people such as Anderson D.D. in Soaps and Detergents:A theroreticaland Practical Review, Miami Beach Fla., 12-14 day in October, 1994, the 6th chapter 172-206 page, editor: L Spitz, AOCS Press, the method of describing in Champaign.
According to considered final application, what propose is to remove the salt dissolving and be derived from the organic impurity of fatty body, the content that removes color, increase glycerol or evaporation glycerol to the processing target of thick glycerol solution.
In order to achieve the above object, especially can be by evaporation, distillation, thermal treatment (to neutralize residual lipid acid), filter subsequently, ion-exchange or ion exclusion processing, reverse osmosis or electrodialysis separate and realize.
For example use multieffect evaporator so that glycerol dilute solution is concentrated.Use triple-effect evaporator and then can evaporate 2.4kg water generates 1kg steam.
Distillation is the one that can be used for the technology of concentrated and purification of glycerol.Because glycerol starts to decompose in the time approaching 202 DEG C (, lower than its boiling point (293 DEG C)), thereby must adopt a low pressure point multistep to distill this glycerine.In some cases, distillation procedure is undertaken by discontinuous operation, until salt and non-volatile biochemical compound fully gather in container.Now shut-down operation was also discharged impurity from container before restarting distillation.Evaporation is carried out under vacuum, can directly obtain concentrated glycerol in the partial condensation (its will prior to water condensation) of the glycerol in device exit.Conventionally for the temperature of 160-165 DEG C, use the pressure of 10mm Hg post, it provides the low glycerol dividing potential drop in vapour phase.
Glycerine through distillation still contains colored compound.For pharmacy or edible purposes, sometimes need this glycerine that decolours.Conventionally gac is joined in glycerine so that its decolouring.
Also developed the glycerin purification by ion exclusion, it utilizes ion exchange resin to separate the ion salt of the aqueous solution that dissolves in non-ionic compound (as glycerol).This technology can be avoided the consumption of heat and chemical regenerant, and only makes water just can flow by the with serious pollution material of purifying as chemical regenerant, as raw glycerine.
Only on acid and basic resin, can be realized exchange by the glycerin solution of salt light contamination.Thereby the glycerol solution of purifying can be concentrated by evaporating thus.
On semi-permeable membranes, be separated into basic reverse osmosis technology by exerting pressure and be used to the concentrated of material stream (especially diluting) in glycerol.
The glycerine obtaining after the transesterify of rapeseed oil and the sodium hydroxide solution in methyl alcohol carries out desalination by film electrodialysis, thereby makes pure glycerin.This technical description is in reference: Schaffner, the people Proc.-World Filtr.Congr.7 such as F. th, volume Two, 629-633 page.
In the method proposing for evaporating glycerin solution, due to some less desirable reaction may occur, thereby the control of temperature requires very strict, for example, because the degraded of the protein existing in glycerine forms nitrogenous compound, form volatility glyceryl ester by reacting with low-molecular-weight soap, the formation of polyglycerol, causes the formation of the finished product propenal frowzy.Thereby restriction residence time at high temperature of glycerine be very important, and this temperature itself is important too.Therefore the evaporation technology, using traditionally can not have the high partial pressures of glycerol in vapour phase.In addition, usually need by multiple treatment combination together with obtain glycerol, the purity of this glycerol and concentration be applicable to anticipation purposes.
The application company has now unexpectedly developed a kind of single-step process, and it can evaporate glycerin solution and also can remove the impurity existing in described solution or produce simultaneously in evaporative process.
Thereby the present invention's object is a kind of method of evaporating glycerin solution (or glycerine) in the fluidized-bed that contains inert solid.
According to the present invention, the described aqueous solution is directly injected in the fluidized-bed that contains inert solid, and described inert solid keeps sufficiently high temperature so that glycerol and water can flash evapns.
As inert solid, can use for example sand, glass or quartz powder, silicon carbide or there is the solid of low specific surface area, the described solid with low specific surface area is being considered to inertia in nature, and it can be made up of aluminum oxide, silicon-dioxide or silica-alumina.Use inorganic salt can't exceed scope of the present invention as inert solid, for example, use sodium-chlor (NaCl), Repone K (KCl), sodium sulfate (Na 2sO 4) or potassium sulfate (K 2sO 4).Described inert solid is preferably selected from sand, silicon-dioxide, quartz, silicon carbide.
Described fluidisation can be guaranteed by the evaporation of glycerol solution, and/or utilize rare gas element (nitrogen, CO 2, circulation gas ...) or the air-flow that forms of air or oxygen or gaseous mixture guarantee.
The temperature of fluidized-bed is generally 220-350 DEG C, is preferably 260-320 DEG C.
Other feature of the present invention and advantage are by by reading specification sheets below and showing better by reference to unique accompanying drawing.
The inventive method obtains the high partial pressures of glycerol in vapour phase, and this demonstrates evaporation glycerol and has advantages of the obviously higher throughput of throughput than distillation obtains under vacuum.
In the methods of the invention, remove the impurity existing in the aqueous solution, this is because fluidization can be taken out (soutirer) part solid continuously it is carried out to dystopy (ex-situ) regeneration simultaneously.The product that in the organic compound existing in glycerol solution and evaporative process, the decomposition of glycerol produces all can cause the formation of coke, and this sedimentation of coke is on inert solid.For example, in the time containing salt in glycerin solution (sodium-chlor or sodium sulfate), these salt are also deposited on inert solid in the evaporative process of glycerin solution.Thereby the inert solid that comprises coke and/or inorganic salt is removed continuously to deliver in another reactor and is reproduced, and then sends back in fluidized-bed.The removal of inorganic salt can be by simply washing solid or any other suitable technology realizes.The manipulation of regeneration of solid comprises burns to solid deposits, and it utilizes air to carry out in a reactor conventionally, and described reactor is for example another fluidized-bed, fixed bed or other any suitable reactor of operation continuously.Preferably use the fluidized-bed of operation continuously.On inert solid, the sedimental burning of carbonization not only can make inert solid regeneration, and can before it returns to the fluidized-bed for evaporating glycerol, be heated.Described burning can for example, be implemented under the existence of fuel (methane), and it contributes to make inert solid to be returned to temperature required while evaporating glycerin solution.
In addition, in fluidized-bed, a particle part is subjected to displacement with respect to another part, causes the friction between solid.In traditional fluidized-bed, make every effort to the friction that limits this consumption solid and manufacture fine particle.And in the methods of the invention, described friction can be eliminated a part and be formed at the settling on inert solid.The fine particle so forming due to friction is removed in downstream, for example, in cyclonic separator or by filtration, separate.
In a unique embodiment in the inventive method shown in the drawings, glycerin solution or glycerine (4) are introduced in the reactor (1) that comprises inert solid fluidized-bed.Described fluidized state can optionally be utilized rare gas element (nitrogen, CO 2, recycle gas ...) or the air-flow of the mixture of air or oxygen or gas guarantee, select described gas so that the composition in (8) is best consistent with the feed in downstream process.Fluidized-bed is by heat exchanger (3) heating.The steam of glycerol and water proposes with (8) from reactor, the fine particle of equipment (7) in can retrieving arrangement.Equipment (6) can wash the solid using in fluidized-bed to remove the inorganic salt of deposition.Reactor (2) is inert solid revivifier, wherein make the solid that takes out from (1) burn existing containing the regeneration gas of molecular oxygen (5) and/or fuel, again transported back reactor (1) through the solid of regeneration.The gas being obtained by regeneration unit is discharged through (9).
Thereby the glycerol steam that method obtains thus can be directly used in the downstream process that need to use gaseous state glycerol, for example be described in propenal or acrylic acid manufacturing process in document WO 06/087083, WO 06/087084, WO 06/114506, WO07/090990 and WO 07/090991, or for as be described in the manufacturing process of vinyl cyanide of application FR 07.53293.Can make equally its condensation, thereby produce the glycerin solution through concentrated and purifying.
The invention still further relates to the fluidized-bed that contains inert solid for evaporating and the purposes of purifying glycerin solution.
To describe in the following embodiments now the present invention, described embodiment only provides to illustrate object, and is nonrestrictive significantly.
Embodiment
The silicon-dioxide of 150g size-grade distribution 100 μ m is put into a fluidized-bed.Described fluidized-bed is that the stainless steel tube that 41mm and total height are 790mm forms by a diameter.Fluidized-bed is immersed in fluidisation sand-bath, utilizes the electric installation being arranged in bath to heat.Three thermopairs record thermograde along described steel pipe.Air-supplied with the flow of 500ml/min (under normal conditions) below an expanded metal, this metal sheet make this treat through gas dispersion at the diameter range of reactor.Mixing solutions/nitrogen to be tested is by leading to until the 0.6mm metal tube of bed body bottom is supplied with, and mass rate is 0.5g/min, and maintain nitrogen flow is 1000ml/min simultaneously.The total pressure of fluidized-bed is 1.2 bar, and temperature remains on 310 DEG C.
The pure glycerol (99.5%, MAT laboratory) that this experiment use aqueous solution contains 18 % by weight and the NaCl salt of 2 % by weight carry out 60 minutes, and it is equivalent to the salt that is supplied to fluidized-bed ingress of total mass 0.6g.
Product collects and concentrates to analyze by specific conductivity in fluidized-bed exit.
The measurement of specific conductivity utilizes Accumet Research AR-20pH meter/conductivity meter type instrument to realize.Result concentrates in following table.
Solution Specific conductivity mS/cm
Pure glycerol 9
Distilled water 5
The aqueous solution that contains 18% pure glycerol and 2% salt 4650
The solution of collecting in the condenser of fluidized-bed exit 15
The total mass of the salt being recovered in condenser is 0.0004g, and it is equivalent to 99.9% efficiency that uses the salt of fluidized-bed to separate, and shows as the weakly conducting rate of the solution of collecting in condenser.

Claims (3)

1. the method for evaporating of glycerin solution in the fluidized-bed that contains inert solid, described fluidized-bed remains on the temperature of 220-350 DEG C, and wherein said inert solid is the solid with low specific surface area that is selected from sand, silicon-dioxide, quartz powder, silicon carbide, aluminum oxide or silica-alumina.
2. method according to claim 1, is characterised in that, described solid is regenerated in second fluidized-bed of continuous operation.
3. the fluidized-bed that contains inert solid is for evaporating and the purposes of purifying glycerin solution, and wherein said inert solid is the solid with low specific surface area that is selected from sand, silicon-dioxide, quartz powder, silicon carbide, aluminum oxide or silica-alumina.
CN200880008695.0A 2007-03-19 2008-03-14 Glycerol vaporization method Expired - Fee Related CN101687743B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0753896A FR2913974A1 (en) 2007-03-19 2007-03-19 GLYCEROL VAPORIZATION PROCESS
FR0753896 2007-03-19
PCT/FR2008/050438 WO2008129208A1 (en) 2007-03-19 2008-03-14 Glycerol vaporization method

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CN101687743A CN101687743A (en) 2010-03-31
CN101687743B true CN101687743B (en) 2014-07-16

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EP (1) EP2121551B1 (en)
JP (1) JP5270586B2 (en)
KR (1) KR101516831B1 (en)
CN (1) CN101687743B (en)
AT (1) ATE476405T1 (en)
BR (1) BRPI0808967A2 (en)
DE (1) DE602008002059D1 (en)
DK (1) DK2121551T3 (en)
ES (1) ES2349395T3 (en)
FR (1) FR2913974A1 (en)
MY (1) MY148567A (en)
PL (1) PL2121551T3 (en)
PT (1) PT2121551E (en)
WO (1) WO2008129208A1 (en)

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FR2920767B1 (en) 2007-09-06 2009-12-18 Arkema France REACTIVE GLYCEROL VAPORIZATION PROCESS
FR2925490B1 (en) 2007-12-20 2009-12-25 Arkema France PROCESS FOR THE SYNTHESIS OF ACROLEIN FROM GLYCEROL
FR2948366B1 (en) 2009-07-22 2012-08-17 Arkema France PROCESS FOR PRODUCING BIO-RESOURCE ACRYLIC ACID FROM GLYCEROL
FR2952056B1 (en) 2009-11-04 2013-01-25 Arkema France GLUTARALDEHYDE BIORESSOURCE AND METHODS OF MAKING SAME
FR2952057B1 (en) 2009-11-04 2011-11-18 Arkema France PROCESS FOR SYNTHESIZING PYRIDINE AND BIORESSOURCE PICOLINES
JP5532842B2 (en) * 2009-11-17 2014-06-25 株式会社Ｉｈｉ Glycerin reforming apparatus and glycerin reforming method
JP5556152B2 (en) * 2009-12-01 2014-07-23 株式会社Ｉｈｉ Glycerin purification apparatus and purification method, glycerin reforming apparatus and reforming method
FR2954311B1 (en) 2009-12-22 2012-02-03 Arkema France PROCESS FOR THE PERFECTED SYNTHESIS OF ACROLEIN FROM GLYCEROL
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CN104707353A (en) * 2015-02-12 2015-06-17 浙江华诺化工有限公司 Glycerin distillation system
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CN110448927A (en) * 2019-07-15 2019-11-15 天津大学 A kind of metabisulfite solution recirculating fluidized bed vaporising device and its operating method

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DE602008002059D1 (en) 2010-09-16
KR101516831B1 (en) 2015-05-04
EP2121551A1 (en) 2009-11-25
PT2121551E (en) 2010-10-11
MY148567A (en) 2013-04-30
JP5270586B2 (en) 2013-08-21
US20100230635A1 (en) 2010-09-16
EP2121551B1 (en) 2010-08-04
DK2121551T3 (en) 2010-11-08
BRPI0808967A2 (en) 2014-08-26
ES2349395T3 (en) 2010-12-30
ATE476405T1 (en) 2010-08-15
KR20090121345A (en) 2009-11-25
JP2010522148A (en) 2010-07-01
WO2008129208A1 (en) 2008-10-30
PL2121551T3 (en) 2011-02-28
CN101687743A (en) 2010-03-31
US8148582B2 (en) 2012-04-03
FR2913974A1 (en) 2008-09-26

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